Process for decontaminating thorium and uranium with respect to ruthenium



i y .evapQra iQn of h Albert e e v y ak i e, an R bert H. R i r, Knoxville, Tenn, assiguors to. the United States of m c as epres tei y the United StatesA' Dm I l 2' :,j

No Drawing, A plication May 20,195.8- ia N 1 ,64& V

- our t i q elates he traces-sin 9f fis i ab d r l m t ia a d mere i u a yi o n i rrovement s me i ns hq iufli nd u ani m values with respect to ruthenium" A'rnai'or act: in th cos f gene a in e e tri i y from n l a s sm i e h rew? t ie ut- .0 mfllii nited States Patent of reducing the operating cost, ofa power-producing.

lea we s o, b ii fiss 'lna'b e' 'h a' a by-product by means of neutron irradiationof fertile thorium 232 or uranium 233,. The value of the fissionable material thusfproduced may thenbe credited to the operatior'icfthe readies b V In the case of humanism, neutron irradiation produces 'fi'ssionabl'emar en by the following-decay chain, v c f ain The? Thorium may be subjected to neutron irradiation in various: types of reactors. For example, thoriunrmet alz sing o'fshort-decayed material, that is, material mans sec

r e eatam at on- As understood in this specification and the appended claims, nitrate ion deficiency is a relative term to indicate thatja solution of a nitrate salt of a metal of a giy n} molarity will not register as high an acidity as a solution of the normal nitrate salt of the same metal molar i-ty, or other words, this is a measure of a s toichiometric deficiency of nitrate ion, which stoichiometric deficiency is made up by hydroxyl ions supplied through hydrolysis. Nitrate ion deficiency in the nitric acidieed solution may be obtained by boiling ed a portion oil the solution to remove nitric acid and oxides: of nitrogen or by the addition of a basic aluminum nitrate s'alt,,"such 'as dibasic allnninum nitrate. This condition is'als maintained in the aluminum nitrate scrub solution eXtr d intoth e organic Vphasealong with thorium and rather than to remain'in the aqueous phase as j The resulting, ruthenium contamination oi? the v th and uranium products has been a limiting factor int rtqwssin o t utwni radia t um- B a se o the. d ic lty w th uth nium d o m n ti o id "other factors, such as the'high level of radioy" of o h r si PrQdu'Q s, neut -i r d th m prqsas n in th as as bee restricted t .lb g-decayed material, that is, materialwhich has been so,

r eiriovewfrom a nuclear reactor and stored for a period 9 a 1. 18 dey Thi la ecay Period h the advantages that'the radioactivity level in the process is grating reduces and that protacti'niurn 233 has largely deca to-the desired product, uranium 233. .However,

has been removed from a nuclear reactor for only 2Q "t 40 days, is more desirable because of the miniinizedf inventory of unprocessed U and the decreased thorium: 22'8factivity "in the product thorium. In the amass-ingot short-decayed material the aqueous phase containing protactinium and fission products is stored 'lloW the 'pr'otactiriiiimto decay 'to U which is subs'eqn'ntly reeovered'f The U thus recovered exhibits level ofisotopic purity;

1011s measures have beenemployed to improve the sep a not; or ruthenium 'frorfrr thorium and uranium. The

liadioactiyefissionroducts H an umand th rium may 1 i e sep r te y e ove ed r meutronrradiate tho ium a s of set n ex n proc ss! described n corp nd ng ppli at on SIN' 69235.86. edteusu 7- 1:25 nt ed: r ess. for 'theseparation q Brqtaet a im Thorium and Uranium from Neutron-Irradiated '-llhg ri-; u Y.-- T- G stwet @1- 11m his presses neut irradi t o um he t rmin metal or th riumio ide s is olved in. trica id andvt e resu t n solution: is adjusted toa e; ion" deficienc n tr te m fiQ en fe d-s u m ia-wn a c buty ph p ate in-v a. dil nt tcu xt aqt he t orium an a um; PIO iQii liUPJ' n ssion-produ ts rema in: e aqueo s c a T e or anicph se is en crr b ith n. a um nmn itra esol t r tim er aminati nofi he qri anium-a e selectiv ly V Puedit and recovered; separately t e th prev of anitrate" ion deficiency as described above Wasd'evised'largel'y to prevent the 'extraetion'of protactini um and ruthenium into the organic phase. While the nitrate iondeficiency has: been "successful "in preventing the. extraction of protactin'ium, excessive amounts of ruthenium: activity werestill being extractedg'particularly :in 'theprocessing of short-cooled material.

Anothenmethod of controlling ruthenium extraction is by digesting the: feed with a ketone and nitriteions in a highly acidified system before the solvent extraction, as

described in co-p'endingL application S.N. 561,962, filed .proved- Ruthenium Decontamination Method? Januany"27 1956-, byA. T. Gresky and entitled Im- This method, ho'wevenfis: inapplicable to a nitrate ion' dejficientsystem, which isrpreferred for processing neutronr adiatee thorium Q lhe r. objects.andadvantagesof our invention will beQapparentfrom the following. detailed description.

"Imaccordance with ourinvention-improved decontamination of thorium and uranium with respect to ruthenium maybe obtained in the organic solvent extraction of a nitratelsolution containing. thorium, uranium, protaetindlfi ssion; products by providing in the nitrate feed splutlori. ionsse lected from the group. consisting; of sulin we wi b l n Q r Pr ss s s aee a method, which is particularly advantageous in the case i of short-decayed, neutron-irradiated thorium. Ruthenium decontamination is improved to such an extent that this element is no longer a limiting factor in the processing of short-decayed material.

The mechanism by which sulfite and bisulfite ions render ruthenium organic-insoluble in a nitrate ion deficient solution is not known. Some evidence had indicated that the organic solubility of organic ruthenium was due to the formation of a soluble complex of ruthenium with nitrite ions which were formed in the solution by irradiation of nitrate ions. For example, it had been found that with non-radioactive materials, the presence of nitrite ions renders ruthenium organic-soluble in a nitrate ion deficient solution, and that the addition of a nitrite-.

destroying agent such as a sulfamate or a peroxide restored the ruthenium to its former organic-insoluble condition. However, we have found that upon allowing such a nitrite-containing solution to stand for a period of several days, or under radiation conditions, agents such thus probably results from radiation eifects other than ni trite formation in the feed solution.

Both sulfite and bisulfite ions are effective in our invention and their source is not critical. These ions may be supplied conveniently from their sodium salts, i.e., sodium bisulfite and sodium sulfite. sodium bisulfite in view of its somewhat higher effectiveness. Any other soluble sulfite or bisulfite may be employed, provided that its cation does not adverselyafiect the extraction process. A suitable ion concentration may also be obtained by introducing gaseous sulfur dioxide into the aqueous feed solution. A

In order to render the ruthenium organic-insoluble, the sulfite or bisulfite must be maintained in contact with the feed solution for a period of time sufficient to allow a We prefer to employ:

reaction between the ruthenium and sulfite or bisulfite The temperature at which the sulfite or bisulfite is contacted with the feed solution is important, particularly in the case of short-decayed material. Because sulfite and bisulfite ions are gradually destroyed by a reaction with degradation products resulting from the high level of.

radioactivity of short-decayed material, it is desirable to keep the contact time to a minimum in order to avoid a complete loss of sulfite or bisulfite. Since shorter contacting times are required at higher temperatures, the highest possible contacting temperature is preferred. However, as the temperature is increased, a point, which may vary with the particular feed solution being processed, is reached at which the sulfite or bisulfite ions are completely and rapidly destroyed by reacting with the nitric acid of hydrolysis. This temperature is generally within the range of C. to 90 C. for the feed solutions presently employed in the processing of neutron-irradiated thorium, that is, solutions constituted of approximately 7 to 8 M nitrate, 1.0 to 2.0 M thorium, 0.4 to 0.6 M aluminum, uranium at a ratio of up to approximately 4000 grams per ton of thorium and smaller quantities of protactinium and fission products, with a nitrate ion deficiency in the solution with the range of 0.1 to 0.2 N. The decomposition temperature depends primarily on the nitrate ion deficiency of the solution and the concentration of the various constituents, the temperature being decreased with an increase in concentration and with a decrease in the nitrate ion deficiency. Since a more exact relationship for determining the critical temperature is not known, we prefer to conduct an empirical test for the particular feed solution involved and to employ a contacting temperature at a safe margin of 5 C. to 10 C. below the critical temperature in order to avoiddestroying the sulfite or bisulfite and at the same time to obtain relatively high decontamination in the subsequent extraction step.

The temperature at which sulfite or bisulfite is destroyed in the feed solution may be determined by withdrawing a sample of the solution, adding 0.006 M sulfite or bisulfite ion, if not already present, and heating slowly. As the temperature increases, portions of the sample are withdrawn at regular temperature intervals, such as at every 3 C. above 55 C. Each portion is then tested for the presence of sulfite or bisulfite by adding a soluble starch solution and titrating with 0.01 M iodine solution. At some definite temperature the sulfite or bisulfite disappears from the solution, as shown by the appearance of the characteristic starch-iodine blue color upon addition of iodine.

At contacting temperatures of 70 C. and above a contacting time of 5 minutes is sufficient to allow the reaction of ruthenium and sulfite or bisulfite. At 65" C. approximately 7 minutes is required, 10 minutes at 60 C.,

. 15 minutes at 55 C. and 20 minutes at 50 C.

Although a short contacting time is important to avoid loss of sulfite or bisulfite in highly radioactive short-decayed material, much longer contacting times may be employed in lower-radiation fields. Thus in the case of long-decayed material the ruthenium and sulfite or bisulfite contacting may be carried out at room temperature, with a contacting time of several days being required.

, The sulfite or bisulfite are less likely to be destroyed by reaction'with radiation degradation products, since the level .of radiation is appreciably lower. However, in view of the shorter time required and the more effective decontamination obtained, it is preferred to perform this contacting at a temperature slightly below the decomposition temperature, at which sulfite or bisulfite is destroyed in the solution, with the same principles for determining the contacting time and temperature applying as for short v decayed material.

Contacting of the sulfite or bisulfite with the feed solution may be performed readily in a continuous column operation by continuously introducing the sulfite or bisulfite into the feedstream and allowing the feed to be held up in a container, such as a conventional hold-up tank, for the time required and at the prescribed temperature. The feed is withdrawn continuously into the solvent extraction columns from the hold-up tank. Any additional apparatus, such as hold-up tanks, required by the present process should, of course, be provided with radiation shielding as is done in the case of the remaining extraction apparatus.

The concentration of sulfite or bisulfite to be employed varies with the type of material being processed. In the processing of long-decayed material, slightly improved ruthenium decontamination is obtained at concentrations as low as 0.001 M. However, for practically effective decontamination a concentration Within the range of 0.01 to 0.2 M is required, and a concentration within the range of 0.02 to 0.03 M is preferred. These relatively low concentrations are preferred since the excess sulfite or bisulfite is eventually converted to sulfate, which has the effect of increasing the loss of thorium to the'aqueous phase during solvent extraction.

For short-decayed material a sulfite or bisulfite conployed, and an initial concentration of approximately order. to .pbtain furtherirutheniumldecontamination it isialsopreferred .to. employ .sulfitenribisulfite ions in the .;aqueous v.aluminum mitra'te..scrub solution :for .both dong and short-decayed material. =:Since .;the ruthenium tin thescrubbing ioperation is .initially -.:in the .organic zphase tno 1 preliminary contacting-treatment .of .the scrub @olution thesulfite oribisuhfite-.is.required. The sulfite or bisulfite is merely .addedatothelscrubsolution, which is then contacted with the organic phase. A sulfite 'or bisulfite concentration Within the range of 0.02 to 1020.6 7 M may .belemployed with approximately 0.03 M

.tbeing prefer'red. xIhe ,scruhbingoperation .may suitably .plbe ..efiected .-.at :the ambient temperature normally employed in the absence of our sulfite or bisulfite treatment. However, somewhat better results are obtained at elevated temperatures and any temperature up to the detcompositon temperature of the sulfite or bisulfite in the :scrub solution may be employed if desired.

It is to be understood that the above-described process may be performed with a plurality of extraction and rscrubbing cycles, with sulfite or bisulfite ions preferably being employed in each cycle.

Our invention is further illustrated by the following specific examples.

EXAMPLE I A laboratory experiment was conducted to determine the effect of added sodium bisulfite on the separation of ruthenium from thorium. A feed solution was prepared zto contain 190 grams of thorium per liter, 0.78 M aluminum nitrate, 0.1 M sodium bisulfite and ruthenium gamma :radioactivity of 10 gamma counts per milliliter per :minute. The nitrate ion deficiency of the solution was 03 N. The solution was heatedfor 5 minutes at 85 C. and cooled to 35 C. The solution was then agitated for .5 minutes and contacted with 5 volumes of 42 percent ttributylphosphate in a kerosenetype diluent. The phases "were separated, and the organic phase was scrubbed with one-half volume portions of a 0.5 M aluminum nitrate solution having a nitrate ion deficiency of 0.15 N. A ggross gamma count made immediately on the scrubbed organic phase showed an activity of only 42 counts per milliliter per minute. This corresponds to a ruthenium decontamination factor of at least 1.6x Control :solutions without bisulfite showed decontamination factors of less than :100.

.A simulated long-decayed thorium feed solution was prepared to contain 1.5 M Th, 0.5 M A1, and about 10 gamma counts per milliliter per minute of ruthenium. The acid deficiency was approximately 0.2 N. Varying amounts of sodium bisulfite were employed in different runs to determine the effect of bisulfite concentration on ruthenium decontamination. The bisulfite was added and the solution was allowed to stand for 5 days at room temperature. In each run the feed solution was stirred for 5 minutes with 42 percent tributylphosphate in a kerosene diluent and the organic phase was scrubbed six times with a 0.5 M aluminum nitrate solution. The results obtained are listed in the following table.

Table l NaHSOa Ru Decon- Concentratamination tion (M) Factor [*Further runs were made the procedure of 'Ex-' ample II- to determine the elfect of .added bisulfite on ruthenium decontamination in acid systems. "With a 3 N acid feed solution there was no beneficial elfect of bisulfite. With ,a 0.5 N acid solution a decontamination factor of 10 .wasobtained, compared to 4 for a.control solution without "bisulfite.

v :IV A pilot plant .runwas conducted ,to determine the eifect of employingbisulfite for ruthenium decontamination of thirty-.day decayed thorium, irradiated to .a level of 4000 grams U per ton of thorium. The thorium was dissolvedin nitric acid, and the solution Was adjusted to an aluminum .nitrate cone.entration of 0.7 M and a nitrate ion deficiency of 0.15 M. Sodium bisulfite was added to produce an initial concentration of 0.01 M, and the solution was heated to slightly below 50 C. for 5 minutes. The feed solution was then contacted wtih tributylphosphate in a kerosene diluent and the organic phase was scrubbed with a 0.5 M aluminum nitrate solution having a nitrate ion deficiency of 0.15 N and a sodium bisulfite concentration of 0.03 M. Two extraction and scrubbing cycles were conducted. For the first cycle ruthenium decontamination factors averaged 8. In the second cycle the ruthenium decontamination factor was 280 for thorium and 1800 for uranium. These values are to be compared with ruthenium decontamination factors of only 2 to 3 for a single cycle without added bisulfite. This experiment was conducted at a temperature and bisulfite concentration slightly lower than optimum for the conditions employed, as may be seen from the following example.

EXAMPLE V Experiments were conducted in a heavily shielded laboratory cell with the short-cooled thorium feed solution of Example IV under the same conditions, except for a higher bisulfite concentration and higher temperatures. Sodium bisulfite was added to produce a concentration of 0.06 M in the feed and the solution was heated to 58 0. instead of 50 C. before extraction. A ruthenium decontamination factor of 320 was obtained for thorium, as compared with 2.5 for a control sample without bisulfite.

It is to be understood that the above examples are merely illustrative and are not to be construed as limiting the scope of our invention, which is limited only as indicated by the appended claims. It is also to be understood that many variations in apparatus and procedure may be employed within the scope of our invention.

Having thus described our invention, we claim:

1. In a process for the separation of thorium and uranium from an aqueous nitrate feed solution containing said elements together with protactinium and fission products which comprises contacting said solution with an organic solvent and separating the resulting organic phase containing said thorium and uranium from the resulting aqueous phase containing said protactinium and fission products, the improvement which comprises providing in said feed solution ions selected from the group consisting of sulfite ions and bisulfite ions.

2. The process of claim 1 in which said ions are bisulfite ions.

3. In a process for the separation of thorium and uranium from an aqueous nitrate feed solution of neutron-irradiated thorium containing said elements together with protactinium and fission products which comprises adjusting said feed solution to nitrate ion deficient conditions, contacting said solution with an organic solution of tributylphosphate in a kerosene diluent, thereby preferentially extracting uranium and thorium into the resulting organic phase while confining protactinium and fission products to the resulting aqueous phase, scrubbing said 5. The method of claim 4 in which the concentrationof said bisulfite ions is within the range of 0.01 to 0.2 M.

6. In a process for the separation of thorium and uranium from an aqueous nitrate feed solution of neutronirradiated thorium containing said elements together with protactinium and fission products which comprises adjusting said feed solution to nitrate ion deficient conditions, contacting said nitrate ion deficient solution with an organic solution of tribut'ylphosphate in a kerosene 'diluent, thereby preferentially extracting uranium and thorium into the resulting organic phase while confining protactinium and fission products to the resulting aqueous phase, the improvement which comprises providing in said nitrate ion deficient feed solution ions selected from the group consisting of bisulfite ions and sulfite ions and maintaining the resulting solution containing said ions at a temperature within the range of approximately 60 C. to 90 C. and below the decomposition temperature of said ions in said solution for a time within the range of approximately 5 to 20 minutes.

References Cited in the file of this patent Proceedings of The International Conference on the Peaceful Uses of Atomic Energy, August 8-20, 1955, vol. 9 pp. 505-510 559-568. United Nations, New York.

UNITED STATES PATENT OFFICE CERTIFICATE 0F CORRECTION Patent No. 2,909,406 October 20, 1959 Albert 3., Meservey et al0 It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, line 62, irradieted thoriwn" insert the two following paragraphs:

therefore, an object of our invention to iovide a method oi improving uranium and thorium decontamination with respect to ruthenium in the extraction of uranium and thorimn from a nitrate solution of neutron-irradiated thorim:o

t from a r 'trate ion de' icient nit" ic acid solution containing the same, together with thorium, uranium protactinium and fission produ ts, into an org nic solvent com rising tributyl=phos -e in a hydrocarbon diluent Another object is to innioit be e traction of ruthenium Signed and sealed this 31st day of Ma 1969.

KARL Ii,

C WATSON Attesting Officer i D Commiss oner of Patents UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2 ,969 ,406

Gctooer 2c, 1959 Albert Tix Meservey et a1n It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, line 62, "irradiated thorium" insert the two following paragraphs;

,3, therefore, an object of our invention to provide 2. method of improving uranium and thorium. decontamination with respect to ruthenium in the extraction of and thorium from a nitrate solution of neutron-irradiated thorium,

Another object is to inhibit the extraction of ruthenium from a ntrete ion deficient nitric acid solution containing the some, together with thorium, protectinium and fission products, into organic solvent corgrising tributyl=phosphnte in a hydrocarbon diluentn Signed and sealed this 31st day of. May 1960.,

test:

KARL Ii, AJCLINE ROBERT 6,, WATSON Attesting Officer Commissioner of P--tents 

1. IN A PROCESS FOR THE SEPARTION OF THORIUM AND URANIUM FROM AN AQUEOUS NITRATE FEED SOLUTION CONTAINING SAID ELEMENTS TOGETHER WITH PROTACTINIUM AND FISSION PRODUCTS WHICH COMPRISES CONTACTING SAID SOLUTION WITH AN ORGANIC SOLVENT AND SEPARATING THE RESULTING ORGANIC PHASE CONTAINING SAID THORIUM AND URANIUM FROM THE RESULTING AQUEOUS PHASES CONTAINING SAID PROTACTINIUM AND FISSION PRODUCTS, THE IMPROVEMENT WHICH COMPRISES PROVIDING IN SAID FEED SOLUTION IONS SELECTED FROM THE GROUP CONSISTING OF SULFITE IONS AND BISULFITE IONS. 